Production of color photographic images



, a 245,788 PRODUCTION OF COLOR PHOTOGRAPHIC IMAGES Jan Jaeken,Hove-Antwerp, and Robert Leopold Jansseune, Wilrijk-Antwerp, Belgium,assignors to Gevaert Photo-Broducten N. Mortsel, Belgium, a Belgiancompany No Drawing, Filed Apr. 3, 1961, Ser. No. 100,010 Claimspriority, application Great Britain, Apr. 6, 1960,

' 12-,163/60 15 Claims. (Cl. 96-9) The present invention relates to theproduction of colored photographic images, more particularly to aprocess of color correction utilizing an integral masking procedure,

I It is known that dyes formed by color development in subtractivemulticolor photographic pictures do not trans -v mit all of the lightwhich practical considerations demand. The cyan dye which should absorbred light and transmit green and blue light usually absorbs a smallamount of green and blue light, as well as a major pro- United StatesPatent layer containing a colorcoupler which is reactive with portion ofred light. The magenta dye which should absorb green light and transmitblue and red light usually absorbs a considerable amount of blue lightand a small amount of red light, as well as a major proportion of greenlight. The yellow dye which should absorb blue light and transmitgreen-and red light is usually satisfactory, Due to the above mentionedunwanted side-absorptions of the dyes formed by color development, it ispractically impossible to obtain a true reproduction of the originalcolors on printing multicolor-photographic transparencies containingsuch dyes.

Correction of the colors on printing is therefor desirable, and this isusually done by masking, Since separate masks are diflicult to registerwith the color transparency, it is desirable that the mask be integralwith the colored images.

A process for the production of a color photographic image wherein themask is integral with the colored image is described in US. patentapplications Ser. No. 705,508, now US. Patent 3,012,884, filed December27, 1957; No. 70,914, now US. Patent 3,013,879, filed November 22, 1960,and No. 72,298, now US. Patent 3,047,385, filed November 29, 1960, byMaurice Antoine de Ramaix and Jan =Jaeken; Ser. No. 66,964, now US.Patent 3,079,256, filed November 3, 1960 by Raphael Karel Van Poucke,Arthur Henri de Cat and Marcel Hendrik Verbrugghe; vand Serial No.71,1l7, filed November 14, 1960, by Jozef FransWillems and I an Jaeken.

According to said'pending applications a color corrected image is formedin a photographic element comprising a silver halide emulsion layer anda color coupler which is reactive withthe oxidation product of anaromatic amino developing agent to form by color development a primarydye image which absorbs a major proportion of light in one region of thevisible spectrum and undesirably absorbs --ar"ninor proportion of lightin at least one other region of the visible spectrum, by treating theexposed and color-developed photographic element with an oxidizingsolution, such as a photographic-bleaching bath, in the presence of acompound, which after oxidation couples with the residual color coupler,whereby a secondary dye image having a gradation opposite to that ofsaid primary dye image, and absorbing light in at least one of saidunwanted minor absorption regions but transmitting substantially all thelight in said major absorption region is formed.

In the last mentioned pending application a method is claimed of forminga color corrected image in .a photographic element having :atlleast .onesilver halide emulsion the oxidation product of the aromatic aminodeveloping agent to form by color development a primary dye image whichabsorbs a major proportion of light in one region of the visiblespectrum, and undesirably absorbs a minor proportion of light in atleast one other region of the visible spectrum, which method comprisestreating said photographic element, after image-wise exposure and colordevelopment, with an oxidizing solution in the presence of a maskforming compound containing a grouping of the following structure:

Ra Ra wherein:

R represents a hydrogen atom or an acyl radical such as an acetylradical,

R represents a hydrogen atom or a functional substituent which issufliciently unstable for being split off during the oxidative coupling,such as e.g. a radical of the formula -CONH or SO X wherein X representsa hydroxyl radical, an amino radical, a substituted amino radical suchas a dialkylamino radical, an heterocyclic radical, an aliphatichydrocarbon radical, a substituted aliphatic hydrocarbon radical, anaryl radical or a substituted aryl radical;

R represents a hydrogen atom, an alkyl radical, an aralkyl radical, anaryl radical or a substituted aryl radical; and

Z represents the non-metallic atoms necessary to com: plete aheterocyclic nucleus containing 5-6 members, -at least one of Which is anitrogen atom.

Now we have found that color corrected images can be formed by treatingan imagewise exposed photographic element comprising a silver halideemulsion layer and a color coupler which is reactive with the oxidationproduct of an aromatic amino developing agent to form by colordevelopment a primary dye image, after the col-or forming development,with a oxidizing solution, such as a photographic bleaching bath, in thepresence of a compound (called hereinafter mask forming compound)corresponding to one of the following general formulae:

as an acetyl radical;

R represents a hydrogen atom or a functional substituent which issufliciently unstable for being split off during the oxidative coupling,such as e.g. a radical of the formula --CONH or ,SO X wherein Xrepresents a hydroxyl radical, an amino radical, a substituted aminoradical such as aidialkylarnino radical, a heterocyclic radical such asa N-rnorpholinyl radical or a N-piperidyl radical, an aliphatichydrocarbon radical, such as an alkyl radical cg. amethyl radical or ahexadecyl radical, a substituted aliphatic hydrocarbon radical, an arylradical, a substituted aryl radical e.g. an alkoxy substituted phenylradical, such as a methyloxy or a hexadecyloxy radical, a carbethoxysubstituted phenyl radical, an alkyl substituted phenyl radical such asa tolyl radical, a carboxy substituted a en ed 15 9 phenyl radical suchas a"2,5-dichloro-phenyl radical,

and an acylarnino phenyl radical;

R represents a hydrogen atom, an alkyl radical such as a methyl radical,a her'adecyl radical or an allyl radical, an arallryl radical such as abenzyl radical, an

aryl radical such asa phenyl or a naphthyl radical or a substituted arylradical such as a methoxy substituted phenyl radical; R representsahy'drogen ator'n, an alkyl radical such as I a methyl radical, ahxadecyl radical, or an' allyl radical, an ar-alkyl radical such as abenzyl radical, an aryl radical such as a phenyl radical or a naphthylradical or a substituted aryl radical such as a methoxy substitutedphenyl radical;

R represents a hydrogen atom, an amino radical, a substituted aminoradical such as a methylphenyl amino radical, an alkyl radical such as amethyl radical oruan ethyl radical, an aralkyl radical such as adihalogenated phenyl radical, an hydroxy substituted phenyl radical, analkoxysubstituted phenyl radical such as a monoor dimethoxy phenylradical or a hexadecyc'loxy phenyl radical, an alkyl mercaptophenylradical, an acyloxyphenyl radical such as a palrnitoyloxyphenyl radical,an acylarninophenyl radical, a dialkyl aminophenyl radical, such'as ap-(N- rnethyl-N-pentadecyl)-arninophenyl radical, an alkylsulfonylphenylradical, or a heterocyclic radicalsuch as a furyl radical, a thienylradical; a pyridyl radical or a 1,3-benzodioxol-5-yl radical;

L and L each represents a methine' group or a nitrogen atom, at leastone of L and L being a methine group;

, Y represents the non-metallic atoms necessary to form an 'heterocyclicnucleus such-as a morpholine nucleus or a piperidine nucleus; and

n is an integer from 1 to 4.

Amidrazones which can be used as mask forming compounds in the processof the present invention and which correspond to the general Formula Iare for instance the compounds listed hereinafter:

Compound R1 R, Br R4 R5 1:

1 Hm s0i -0H3 CmHaa Goon. r

coon i e a CH;

2 H- -SOQOOHS cH= -Cm u C OCH: r

a zC1s a-: CH; -cu,-C r

5 3 3 6 Q Q 7; H.-. sm-coon cu= 41mm, -c1 n s 11.-- -o0NH, 0Hi warn,Gwen: 1

9 11.- 4024210113, ciH5 0zHi ocrn 1 10 H..-. s'0l-C 000H 0H; -016HflGoon,

dour

OCHs 11 H S02 'CH: CioHu OOCHQ L bin-s0 SOzOH benzyl radical, asubstituted benzyl radical such as a methoxy substituted benzyl radical,an alkylene radical such as a methoxy styryl radical, an arylradi-Amidrazones which can be used as mask forming compounds in the processof the present invention and which correspond to the general Formula IIare for in cal, a substituted aryl radical such as a monoor stance thecompounds listed hereinafter:

9 .Mask' formingv compounds having two. groups which can be split offduring the oxidative coupling are e.g.:

use? CzHs The amidrazone compounds having the general For-- mulae I andII- can: be synthetized according to H. Bredereck, Ber. 92, 837-849(1959), according to the reaction. scheme 10 carbazide. orthiosemicarbazide in alkaline medium. The reaction: scheme is thefollowing:

wherein: R R and'R have the same significance as indicated in thegeneral Formulae I and II.

On carrying out the second step of. the latter reaction with hexadecylsulfonyl hydrazide instead of semicarbazide a non-migratory maskcompound is obtained. As starting materials thioamides can be used whichare prepared accordingtosuificiently known. methods. Examples ofthesemethods are e.g. the method indicated as the Wilgerodt-Kindler' reactiondescribed by M. Carmack in Org. Reactions, vol. 3, p; 83/107, edited byR. Adams, John Wiley and Sons, New York (1946), and the transformationof amides into thioamides in pyridine by means of phosphoruspentasulfide described by E. Klingsberg,

J.A.'C.S. 73, p'. 4988 (1951).

Byway ofexample the preparations of some mask compounds of the presentinvention are given hereinafter.

PREPARATION l N-phenyl-Z,6-dimethyl pyridone- (4 )-hydi'az0r te-dihydr0-chloride This compoundcan be-prepared according, to S. Hiinig. andG.Kobrich, Ann. 617, p. 194 (1958)..

. PREPARATION .2. N ;N dz'nrethyl N '-n-hexadecylsul fonylformamidrazone HCN(CH N-NH-Soz onz wcn A solution of26g. (0.75 mol) ofn-hexadecyl'sulfonyl chloride in 280 cm. of ether is added dropwise to asolution of an exoess of hydrazine hydrate (40 cm?) in 200 em. ofethanol at temperature of 25 C; After stirring for min, 120 cm. of waterare added to this solution. Then-hexadecyl sulfonyl' hydrazide crystalsthus obtained are suckedoff: and washed with a? mixture of water andethanol (1:3 by weight).

After drying an recrystallizat-ionafromacetonitrile, 24 g. ofn-hexadecyl sulfonyl hydrazide melting at.89 C. are obtained.

A, solution of 2.31: gof phosphorus oxychloride (0.0050 mol) in 4 cm. ofanhydrous benzene is added? to a solution of 3.65 g. (0.0050 mol) ofdimethylformamide in 4 =cm. of anhydrous benzene at a temperature: of C.This mixture is kept overnightatroom temperature. Next, asuspension of 4g. (0.0125 mol) of n-hexadecylsulfonylhydrazide in cm. of anhydrousbenzene, prepared as described hereinbefore, is admixed at 2025 C. Afterstirring for 5 h. and storing for 12 h., the resulting hydrochloride isprecipitated with ether, sucked off and Washed'with ether. 5.8 g. of ahydrochloride melting at 150 C. (with decomposition). is obtained: Thebase is set free by introducing said hydrochlorideinto water,neutralizing with sodium bicarbonate and extracting. with benzene. Next,this benzene solution is evaporated under reduced pressure at 40 C., andthe resulting residue is washed with ethanol. 1.4" g. of N ,N dimethyl N-n hexadecylsulfonyl formamidrazone melting at 89 C. are Obtained. Thismelting point does not rise after recrystallization from methanol orfree acetonitrile.

PREPARATION 3 N ,N -cyclodiethylene oxide-N-n-hexadecylsulfonylthieneamidrazone H O G H OHz-CE:

CHrCHa NNHSO 2-(0 H2) -43133 5.6 g. (0.050 mol) of 2-thiopheno aldehyde,2.4 g. (0.075 mol) of sulfur and 6.5 g. (0.075 mol) of morpholine areheated .for 3 h. on a water-bath. After pouring the reaction mixtureinto 100 cm. of water, sucking off, ,washing with water and drying, 11.5g. of 'a product melting at 72 C. are obtained. After recrystal--lization from isopropanol, 7.8 g. of thiothieno morpholide meltingconstantly at 77 C. are obtained.

A solution of 2.13 g. (0.010 mol) of this compound in 15 cm. of acetoneis refluxed for 1 h. with 2 cm. (0.030 mol) of methyliodide. Theresulting 'precipi-- tate is sucked off and washed with acetone. 3.8 g.of 4-(alpha-methylthiothienylidene) morpholinium iodide melting at 163C. (with decomposition) are obtained.

1.95 g. (0.0055 mol) of this morpholinium iodide and 1.6 g. (0.005 mol)of n-hexadecylsulfonyl hydrazide, prepared as described in Preparation2, are allowed to react for 24 h. at room temperature in 18 cm. ofpyridine. After pouring this reactionmixture into 100 cm. of water,sucking ofi, washing with water and drying, 2 g. of a product melting at60 C. are obtained. After re-- crystallization from methanol 1 g. of N,N -cyclodiethylene oxide-N -n-hexadecylsulfonyl thienamidrazone -melt-'ing at 78 C. is obtained.

PREPARATION 4 N ,N -cyclodiethylene oxide-N -hexadecylsulfonyfbenzamidrazone 9.65 g. (0.0275 mol) of4-(alpha-methylthiobenzylidene)-morpholinium iodide prepared accordingto D. Peak, J. Chem. Soc. (1952), 4067-75, and 8 g. (0.025 mol) ofn-hexa-decylsulfonylhydrazide prepared according to Preparation 1, areheated for 2 h. at C. in a mix-. ture of 95 cmfiof pyridine and 5 cm. ofpiperidine. Next the reaction mixture is poured out into 500 cm. ofwater. The precipitate formed is sucked off, washed with water anddried. 11.7 g. of product melting on sharply at 80 C. are obtained.After recrystallization from methanol 8 g. of N ,N -cyclodiethyleneoxide-N, -n-: hexadecylsulfonyl benzamidrazone melting at 94? C. forobtained.

PREPARATION 5 N ,N -cycl0diethyleneoxide-N -n-hexadecylsulfanyl phenylacetamidrazone /CH2-CE: H CHz-CH: N-NH-SOr-(CHzha-CHa 1 g. (0.0027 mol)of 4-(l-methylthio-2-phenyl ethyl-3 idene)-n1orpholinium iodide,prepared according to Dr. Peak, J. Chem. Soc. (1952), 4071, and 0.8 g.(0.0025 mol) of n-hexadecylsulfonyl hydrazide .are allowed to re-- actfor 24 h. at room temperature in 20 cm. of pyridine. After pouring thissolution-into water and recrystallization from methanol 0.5g. ofamidrazone-melting at 79 C. is obtained.

PREPARATION 6' N ZN -cyclopentyl-N (4-carboxyphenylsulfonyl -3-meth0xy-4-n-hexadecylbenzamidrazone /CHz-Cgz I N-NHSOr- OCH3.

7.5 g. (0.33 mol) of sodium are dissolved in 750 cm. of methylCellosolve (trade name for ethylene glycol monomethylether). Afteradding 50 g. (0.33 mol) of 3-methoxy-4-hydroxybenzaldehyde and refluxingthe reaction mixture until complete dissolution of the reactants g. (0.3mol) of n-hexadecylbromide are dropwise added. After further. heatingfor 1.5 h., the reaction mixture is cooled and 'suckedotf. The filteredcrystals are then recrystallized from methanol yielding 86 g. of 3methoxy 4 n hexadecyloxybenzaldehyde. Melting point: 69 C.

A mixture consisting of 9.4 g. (0.025 mol) of this aldehyde, 1.2 g. offlowers of sulfur and 3.7 cm'. (0.038 mol) of piperidine is heated for 6h. on a water-bath. After .cooling, the product obtained is ground underwater, sucked off, washed with water and recrystallized from ethanolyielding 9.7 g. of 3-methoxy-4-n-hexadecyloxybenzothiopiperidine.Melting point: 67 C.

A mixture consisting of 38 g. (0.08 mol) of this compound, 16 cm. (0.24mol) of methyl iodide and 160 cm. of anhydrous acetone are refluxed for1 h. After sucking off and washing with ether 41.5 g. ofl-alpha-methylthio 3-methoxy-4-r1-hexadecyloxy benzylidene-piperidiniumiodide are obtained. Melting point: 90 C. (with decomposition). Onrecrystallization the product is unstable.

6.17 g.. (0.01 mol) of this compound dissolved in 50 cm. of pyridine areallowed to react for 12 h. at room temperature with 2.16 g. (0.01 mol)of 4-carboxyphenyl sulfonyl hydrazide. After. pouring into ice, suckingoff, washing with water and recrystallization from acetonitrile, 3 g. of'N ,N -cyclopentyl-N -(4-carboxyphenylsulfonyl)- 3 methoxy4-N-hexadecyloxybenzamidrazone are obtained. Melting point; 108 C.

The 4-carboxyphenyl sulfonyl hydrazide used in the above preparation isobtained by first dissolving 11 g. (0.05 mol) of 4-carboxyphenylsulfonylchloride in 650 COOH ' cm. of anhydrous ether and by adding thereto at-5 C.

N ,N -cyclopentyl-N -n-hexadecylsulfonyl-3-methoxy-4-hydroxybenzamidrazone CHz-CHz N HOO \CH2-C2 (I) 0 H3 N-NHS O r( 2)1s z8.75 g..(0.0575 mol) of 3-metl1oxy-4-hydroxybenzaldehyde and-5 0111.3(0.050 mol) of piperidine are reacted for 8 h. at C. with 2.4 g. (0.075mol) of sulfur. The

' sticky mass is cooled and transformed into a powdery substance byadding water thereto. This powder is sucked oii and washed with wateruntil neutral. The crude product obtained is recrystallized. frompetroleum naphtha (boiling range. 90-120) yielding 7 g. of 3-methoxy-4-hydroxybenzothiopiperidide. Melting point: 118 C. Re-

1.3 crystallization from ethylaeetate raises the melting point to 119 C.p 15 g. (0.06 mol) of the foregoing thioamide are refiuxed for 1 h. with17 cm. (0.28 mol) of methyliodide in 177 cm. of anhydrous acetone.

After cooling the reaction product is sucked off and washed with etheryielding 23 g. of 1-(alpha-methylthio- 3methoxy-4-hydroxy-benzylidene)-piperidinium iodide. Melting point: 176C. (with decomposition). The prodnot is unstable on recrystallization.

23 g. (0.06 mol) of the foregoing iodide salt are reacted at roomtemperature for 12 h. with 18.4 g. (0.06 mol) of n-hexadecyl sulfonylhydrazide dissolved in 230 cm. of pyridine.

After pouring out the reaction mixture on ice, the solidified product isWashed with water and recrystallized from ethanol. 25 g. of N ,N-cyclopentyl-N -n-hexadecyl sulfonyl 3 methoxy-4-hydroxybenzamidrazoneare obtained. Melting pointi 93 C.

PREPARATION 8 A mixture consisting of 13.6 g. (0.1 mol) ofp-methoxybenz'ald'ehyde, 4.8 g. (0.15 mol) of flowers of sulfur and 13cm. (0.15 mol) of morphoiine is refluxed for 3 h. on a water-bath. Aftercooling, sucking off, washing with water and recrystallization fromethanol, 20.5 g. of 4- methoxybenzothiomorpholide are obtained. Meltingpoint: 109 C. A further recrystallization does not alter the meltingpoint.

A mixture consisting of 11.8 g. (0.05 mol) of this thiomorpholide, 50cm. of anhydrous acetone and 5 cm. (0.05 .mol) of methyl iodide isrefluxed for 1 h. The precipitate formed is sucked ofi and Washed withether to yield 18.5 g. of4-(alpha-methylthio-4-n1ethoxybenzylidene)-morpholiniurn iodide. Meltingpoint: 152 C. (with decomposition). On recrystallization this product isnot stable.

1.04 g. (0.00275 mol) of this morpholinium iodide is reacted for 12 h,at room temperature in a mixture of 35 cm. of pyridine and 0.8 g.(0.0025 mol) of n-hexadecylsulfonyl hydrazide. The reaction mixture ispoured into ice. The formed crystals are sucked off, washed with waterand recrystallized from ethanol to yield 1 g. of N N cyclodiethyleneoxide N -n-hexadecylsulfonyl-4-me thoxybenzarnidrazone. Melting point:69 C.

PREPARATION 9 N ,N -cycldiethylene oxid-N -n-lzexadecylsulf0nyl-2,4-dichlorobenzamidrazbne To a chilled solution of 6 g. (0.15 mol) ofsodium hydroxide in 50 crn. of Water are first added at 0 C. 11 g.(0.125 mol) of morpholine, and then at 0 to C. 26.2 g. (0.125 mol) of2,4-dichlorobenz'oylchloride. After adding the reactants the reactionmixture is stirred for another hour at the same temperature. Aftersucking off, washing until neutral with water and recrystallization frompetroleumnaphtha, 24 g. of 2,4-dichloro-benzomorpholide are obtained.Melting point: 94 C.

5.2 g. (0.02 mol) of this morpholide in a mixture of 25 cm. of pyridineand 1.8 g. (0.008 mol) of phosphorus pentasulfide are refluxed for 40min. After pouring the reaction mixture into ice the formed precipitateis sucked off, washed with water and recrystallized from ethanol toyield 4.5 g. of 2,4-dichlorobenzothiomorpholide. Melting point: 148 C.

34.5 g. (0.125 mol) of this thiomorpholide dissolved in 22.5 cm. (0.375mol) of methyliodide are refluxed for 1 h. After sucking oil, 20 g. of4-(alpha-methylthio-2,4- dichlorobenzylidene)-morpholinium iodide areobtained. Melting point: C. (with decomposition). This product iunstable on recrystallization.

55 g. (0. 13 mol) of this product dissolved in 750 cm. of pyridine arereacted at room temperature for 48 h. with 39 g. (0.12 mol) ofn-hexadecylsulfonylhydrazide. After pouring this reaction mixture intoice, sucking otf, washing with water and recrystallization, 54 g. of N,N cyclodiethylene oxide-N-n-hexadecylsu-lfonyl-2,4-dichlorobenzamidrazone are obtained. Meltingpoint: 70 C.

PREPARATION 10 w N -methyl-N -pl ienyl-N -n-hexadecylsulfohybb'enzamidrazone PREPARATION 11 N ,N -cycl0diethyleneoxide-N-n-hexadecylsulf0nylz-chlorob'enzamidrazone To a chilled solution of 6g. (0.15 mol) of sodium hydroxide in 50 cm. of water are first added at0 C. 11 g. (0.125 mol) of morpholine and then at 0 to 5 C. 22 g. (0.125mol) of o-chlorobenzoylchloride. After the addition of the reactantsstirring is continued for /2 h. at the same temperature. The productformed is filtered off and washed with water until neutral.Recrystallization from petroleum naphtha yields 20 g. of2-chlorobenzomorpholide. Melting point: 73 C.

14.5 g. (0.065 mol) of the preceding amide are reacted at refluxtemperature for 40 with 5.8 g. (0.026 mol) of phosphorus pent-asulfidein 65 cm. of pyridine. After pouring out the reaction mixture in ice,sucking off, washing with water and :recrystallizing from ethanol 11 g.of 2chlorobe-nzothiornorpholide are obtained. Melting point: 124 C.

11 g. (0.045 rnol) of the preceding thioamide are refiuxed for 1 h. with8.8 cm. (0.15 mol) of methyliodid'e in 40 cm. of anhydrous acetone.After cooling, the formed reaction product is sucked off and washed withether to yield 16 "g. of 4--(alpha-methyl-thio-2-chlorobenzylidene)-morpholini urn iodide. Melting point: 152 C. (with decomposition). Theproduct cannot be recrystallized because it is not stable enough.

16 g. (0.04 mol) of the preceding morpholinium iodide are reacted atroom temperature for 48 11. with 11.5 g.

(0.036 mol) of nhexadecylsulfonylhydraziide in 220 cm. of pyridine. Thereaction mixture is poured into ice and the precipitate formed is suckedotf, washed with water and recrystallized from nhexane to yield 17 g. ofN ,N

PREPARATION 12 N -methyl-N -n-hexadecyl-N (4'-carboxyphenylsul fonyl -3,4 -dim'etl txy benzamidrazone C H;

z C a0--- 915- 3 To a solution of 25.5 g. (0.1 mol) ofmethyl-n-hexadecylamine in a mixture of 250cm. of diox-ane and 22.5

cm. (0.11 mol) of N sodium hydroxide is added drop-- wise at 20 C. asolution of 20.5 g. (0.1 mol) of 3,4- dimethoxybenzoylchloride in 50 cm.of dioxane. After stiring this mixture for 1 h. 125 cm. of water areadded. The formed oily layer is dried on sodium sulfate and d stilledunder reduced pressure. Boiling point: 236- 240 C., 0.4 mm. of Hgpressure. Yield: 34- g. of 3,4- dimethoxy-benzoicacid-methyl-n-hexadecylamide.

45 g. (0.1 mol) of the preceding amide are refluxed for 2 h. with 24 g.(0.1 mol) of phosphorus pentasulfide in 100 0111. of pyridine. ingsodium chloride, the coagulated product .is sucked off, washed withwater and recrystallized from acetonitrile to yield 34 g. of3,4-dimethoxyabenzothio-methyl nhexadecylarnide. Melting point: 63 C.

g. (0.023 mol) of the preceding thioamide are dissolved at roomtemperature in 10 cm. of methyliodide. Immediately after completedissolution ether is added and the solution is left for 12 h. in arefrigerator. 6.1 g. of

alpha-methylthio 3,4 di-methoxy-henzylidene-methyl-nhexadecylammoniumiodide are obtained. Melting point: 100 C. (with decomposition). Theproduct is unstable and cannot be purified by recrystallization.

13.5 g. (0.0234 mol) of the preceding compound are allowed to react for72 h. .at room temperature in 50 cm. of pyridine with 5.05 g. (0.0234mol) of 4-carboxyphenylsulfonylhydrazide. The solvent is distilled offand the residue is left under Water to solidify. The solidified productis freed from water by sucking cit and recrystalg l-ized from ethanol toyield 8 g. of N methyl-N -n-hexadecyl-N -(4 carboxyphenylsulfonyl)3,4dimethoxybenzaimidrazone. Melting point: 142 C.

, PREPARATION 13 N -methyl-N -n-hexadecyl-N (4'tolusulfonyl) -4- methoxybenzamidrazone yields 70 g. ofp-n1ethoxybenzoyl-N-methyl-N-n-hexadecylarnide. Melting point: 50 C.

15 g. (0.04 mol) of this amide are refluxed for 40 min. with 4 g. (0.016mol) of phosphorus pentasulfide in 150 cm. of pyridine. The reactionmixture is poured on ice and the solidified material formedis suckedoff, washed with water and recrystallized from ethanol to yield 13.5

After pouring into ice and add-' Whilst stirring at 10 C., 41 g. (0.24mol) of 16 g. of 4-methoxybenzothio-N-methyl N n=hexadeeylamide. Meltingpoint: 63 C.

13.5 g. (0.033 mol) of this thioam-ide are refluxed for 1 hf. with 13.5cm. (0.02-2'mol) of methyliodide in ctn. of acetone. After distillingoff the'solvent and washing the residue with the ether, 17 g. ofvalpha-methylthio- 4-methoxybenzylideneamethyl-n-hexadecyl ammoniumiodide are obtained. Melting point: C. (with decomposition).This'product is not stable enough for being purified byrecrystallization.

11 g. (0.02 mol) of this compound are reacted for 12 h. at roomtemperature with 3.7 g. (0.02 mol) of p-tolusulfonylhydrazide in 70 cm.of pyridine. The reaction mixture is poured on ice; Theprecipitatezformed is Washed'with water :and recrystallizedfromxmethanol to yield 8 g. of N methyl N n hexadecyl N (4-tolusulfonyl) 4 methoxybenzamidrazone. Melting point: 66 C.

PREPARATION 14 N -phenyI-N -allyI-N -(4'-t0lusulfonyl)-benzamidrazoneMHSOP CH.

To a boiling solution of 13.3 g. (0.1 mol) of N-allylaniline in tolueneis dropwise added a solution of 14 g. (0.1 mol) of 'benzoylchloride in50 crn. of toluene insuch a rate that. the toluene on being distilledover carries off the formed :hydrogen'chloride. This. reaction is comtin-ued for 8 h., during which period toluene is added for maintainingthe liquid volume constant. After distilling oil the solvent the residueis distilled under reduced pressure to yield 15 g. of-N-allylbenzanilide. Boiling range: 134138 C./0.6 mm. of Hg pressure.

76g. (0.32 mol) of this anilide are allowed to react for 40 min. with44.5 g. (0.2 mol) of phosphorus pentasulfide in 450 crn. of pyridine.The reaction mixture is poured on ice, washed with a sodium sulfidesolution and with water. Recrystallization from n-hexane yields 57 g. ofN-allyllbenzothioanilide. Melting point: 69 C.

5 g. (0.02 mol) of this thioanilide are reacted for 12 h. at roomtemperature With 15 cm. of methyliodide. After sucking oil the solidproduct and washing with acetone, 7.2 g. of alpha-methylthiobenzylideneN-allylanilinium iodide are obtained. Melting point: 180 C. (withdecomposition). -For the product is not stable enough it cannot bepurified by recrystallization.

4 g. (0.01 mol) of the preceding compound and 1.7 g. (0.03 mol) ofpotassium hydroxide dissolved in 40 cm. of anhydrous ethanol are reactedfor 24 h. at roorntemperature with 1.86 g. (0.01 mol) ofp-tolusulfonylhydrazide. After evaporating under reduced pressure at 30C., the residue is first Washed with water and next with ethanol inorder to obtain a solid product. After recrystallization from methanol1.3 g. of N -phenyl-N allyl-N (4'-tolusulfonyl)'-'benzamidrazone areobtained. Melting point: C.

PREPARATION 15 88.2 g. (0.3 mol) of dibenzoylpiperazine preparedaccording to vA. V. Hofrnann, Ber. 23, 3301 (1890), are-re fi-uxed for 2h. with 80 g. (0.36 mol) of phosphorus pentasulphide in 200 cm. ofpyridine. The reaction mixture is poured on ice, sucked ofi, washed withan aqueous sodium sulphide solution and with water. By boiling thewashed precipitate in carbon disulphide and by recrystallizing fromdichloroethane 6 g. of dibenzothiopiperazide are obtained. Meltingpoint: 275 C. (unsharp).

1.83 g. (0.005 mol) of this product is refluxed for l h. with 3.6 cm.(0.06 mol) of methyliodide in 40 cm. of dichloroethane. The reactionmixture is sucked off and the solid product obtained is washed withdichloroethane to yield 3.1 g. of 1,4-di(Q-methylthiobenzylidene)-piperazonium iodide. Melting point: 190 C. (withdecomposition). This product is unstable and cannot be purified byrecrystallization.

7.2 g. (0.12 mol) of the foregoing compound are allowed to react for 24h. at room temperature with 7.5 g. (0.24 mol) ofn-hexadecylsulfonyhhydrazide in 150 cm. of pyridine. The reactionmixture is poured on ice, the solid product formed is sucked off, washedWith water and next with methanol. Recrystallization frommethyl-ethyletone yields 7 g. of N N N N diethylene di (N nhexadecylsulfonylbenzamidrazone). Melting point: 141 C.

' @nt r A solution in cm? of Warm ethanol of 1.99 g. (0.005 mol) ofN,N'-dimethyl-N,Ndiphenyl-S-methylisothiouronium iodide, preparedaccording to D. Peak, J. Chem. Soc., 4072 (1952), is dropwise added to0.25 cm. (0.005 mol) of hydrazine hydrate whilst heating on awater-bath. Heating is continued for 2 h. and air is bubbled through thereaction mixture until no more methylmercaptane is formed. Afterevaporation to dryness, the residue is washed with ether andrecrystallized from isopropanol. 1 g. of N,N-dimethyl-N,N-diphenyl-N"-amino-guanidine is obtained. Melting point: 182 C.

According to a preferred embodiment of the present invention, the maskforming compound is incorporated in one of the layers present in thelight sensitive photographic material, preferably in the silver halideemulsion layer whereinthe mask image is to be formed by oxidativecoupling of the residual color coupler, present in that layer, with themask forming substance; in order to prevent the diffusion of the maskforming compound out of the silver halide emulsion layer wherein thiscompound originally Was incorporated, preferably mask forming compoundsare used containing a radical (e.g. the radical X and/or R in the aboveformulae) com prising a linear chain of 5 to carbon atoms.

The process of color correction of the present invention may bepractised i.e. by using a color photographic material containing acoupler for magenta belonging to the class of the pyrazolone orindazolone color couplers and/or a coupler for cyan belonging to theclass of the phenol or naphthol color couplers. Depending upon thestructure of the color coupler used in combinationwith the mask-formingcompound according to the present invention, yellow to magenta coloredmask images are obtained on treating the photographic material with anoxidizing substance such as present in a potassium ferricyanidebleaching bath.

It has been found that by oxidative coupling of the mask-formingcompounds of the Formula II above with a pyrazolone or indazolone colorcoupler for magenta, a yellow colored mask image is obtained whichcompensates the undesirable side-absorption in the blue part of thespectrum of the magenta dye image obtained by 18' color development ofthe exposed areas of the layer containing said coupler for magenta.

It has further been found that by oxidative coupling of the mask-formingcompounds of the Formula I or II above with naphthol color couplers forcyan, a yellow to magenta colored mask image is obtained whichcompensates the undesirable side-absorption in the blue and green partof the spectrum of the cyan image obtained by color development of theexposed areas of the layer containing said cyan coupler. Naphthol colorcouplers which are especially useful for obtaining a mask image byreaction with the mask forming substances according to the presentinvention are e.g. those represented by the general formula:

(.FH ill-D o O-NII- i SOaM Z wherein:

X represents a member selected from the group consisting of an oxygenatom, a sulfur atom, a NHCO group, a CONH group, a SO NH- group, a NH-SOgroup, a -N-alkyl group and asulfonyl group;

Z represents a member selected from the group consisting of a hydrogenatom and a halogen atom;

D represents an aliphatic radical comprising a linear chain of at least5 and at most 20 carbon atoms, preferably 14, 16 or 18 carbon atoms;

M represents a member selected from the group consisting of a hydrogenatom, an alkali metal atom and an ammonium group.

Suitable color couplers of the above general formula are for instance:

N-(2-n-hexadecyloxy-5-sulfo)' phenyl 1 hydroxy-2- naphthoic acid amidesodium salt, N(2-n-hexadecyloxy 5 sulfo) phenyl-1-hydroxy-4-chloro-Z-naphthoic acid amide sodium salt, N-(2-n-hexadecylmercapto5sulfo) phenyl-l-hydroxy- 2-naphthoic acid amide sodium salt,N-(2'-n-hexadecylmercapto-5-sulfo) phenyl-l-hydroxy- 4-bromo-2-naphthoicacid amide sodium salt, N-(2-n-hexadecylmercapto-5'-sulfo)phenyl-l-hydroxy- 4-chloro-2-naphthoic acid amide sodium salt,N-(2-palmitoylarnino 4' sulfo) phenyl-l-hydroxy-Z- naphthoic acid amidesodium salt, N-(2-methyl cetylamino-5'-sulfo )-phenyl 1 hydroxy-4-chloro-Z-naphthoic acid amide sodium salt,N-('6'-n-hexadecylsulfonylphenyl)-1-hydroxy 2 naphthoic acidamide-3-sodium sulfonate, N-(6-n-hexadecylsulfonylphenyl') 1hydroxy-4-chloro- Z-naphthoic acid amide-3-sodium sulfonate, N-(4-nhexadecylsulfonyl)-1-hydroXy-2-naphthoic acid amide-3-sodium sulfonate.

These col'or couplers for cyan can be prepared eg by condensation ofl-hydroxy-Z-naphthoic acid or its derivatives with the suitable aromaticamines according to US. patent application Serial No. 66,289, filed'October 31, 1960, by Arthur Henri de Cat, Raphael Karel Van Poucke andHector Alfons Vanden Eynde.

It is to be noted that by oxidative coupling of some of the amidrazonemask forming compounds of the Formula I or 11 above with color couplersfor cyan of the formula given above, a yellow to orange colored maskimage is obtained which compensates the undesirable side-absorption inthe blue as Well as in the green part of the spectrum.

For carrying out the process according to the present invention, thecolor couplers and mask compounds can be incorporated into aphotographic silver halide emulsion prepared by means of the colloidsusually employed therefor, such as for instance gelatin, polyvinylalcohol, cl-' lodion or other natural or synthetic colloids. The silverhalide emulsion can be coated on a support consisting of paper, glass,nitrocellulose, cellulose esters such as cellulose triacetate,polyester, polystyrene or another natural or synthetic resin, and formspart of a photographic material with one or more emulsion layers. Themultilayer material usually comprises the following elements: a support,a red-sensitive emulsion layer having a color coupler for cyan, agreen-sensitive emulsion layer having a color coupler for magenta and ablue-sensitive emulsion layer having a color coupler for yellow. Thereis a yellow filter composed in most of the cases of a gelatin layercontaining dispersed colloidal silver, located between theblue-sensitive emulsion layer and the green-sensitive emulsion layer. Itis not only possible to incorporate the color couplers into thelight-sensitive silver halide emulsion layer itself but they can also beincorporated into an adjacent non-light-sensitive colloid layer or intoa nonlight-sensitive layer which is separated from the lightsensitiveemulsion layer by a water-permeable colloid layer.

The process according to the invention proceeds as follows: silverhalide is reduced to silver at the exposed areas in a color developingbath containing a primary amine aromatic developing agent which is atthesame time oxidized. The oxidized developing agent reacts with thecolor coupler and forms a dyestuff, the. mask forming compound accordingto the invention not being affected. After the color development, thematerial comes into the bleaching bath wherein the oxidation of the maskforming compound takes place. The remaining color coupler stillavailable at the non-exposed areas of the material couples oxidativelywith the oxidation product of the compound thus formed whereby thecolored mask is formed. Subsequently, the photographic color material iswashed with water, fixed and dried.

The following aromatic amino-compounds can be used as developers forsuch material: mono-, diand triamino-aryl compounds, more especiallyN,N-dialkyl-pphenylenediamines, such as N,N diethyl p phenylenediamineand N,N-diethyl-2-methyl p-phenylene diamine,-

and derivatives thereof such as N,N-dialkyl-N-sulfomethylorcarboxymethyl-p-phenylenediamine. As useful monoamino-developers shouldbe cited: aminophenols and aminocresols or their halogen derivatives andalso the amino-naphthols.

The bleaching bath generally contains potassium bro- EXAMPLE I To /2 kg.of a red-sensitive silver bromo-iodide (2% iodide) emulsion containing/6 mol of silver halide are added: (1) a 10% aqueous solution containingas a color coupler for cyan 7 g. of 1,2-hydroxy-naphthoic acid-4-sulfo-2-n-hexadecylsulfonyl anilide, prepared according to a methoddescribed in our Belgian patent specification No. 584,846, and cm. of 2N sodium hydroxide, and (2) 2 g. of N ,N .-cyclodiethylene oxide-N-n-hexa decylsulfonyl benzamidrazone prepared as described inPreparation 4, dissolved in 10 cm. of ethylene glycol monomethylether.Next, the emulsion is acidified with N acetic acid to pH=5.8 and broughtto a volume of 1 litre by admixing water. After coating this emulsiononto a film support, the light-sensitive material thus obtained is.

exposed through a grey-wedge with a constant 0.15, and

then developed for 9 minutes at 20 C. in a color developing bath of thefollowing composition:

Water to 1000 cm. (pH:

This material is rinsed for 30 minutes at 18 to 20 C. and fixed for 5minutes at 20. C. in a fixing bath of the following composition:

G. Sodium thiosulfate 200 Sodium bisulfite 25 Potassium alum 20 Sodiumbiacetate 20 Boric acid 7.5

Water to 1000 cm. (pH: 4).

Next, the material is rinsed again for 10 minutes at 18 to 20 C. andtreated for 5 minutes in a bleaching bath of the following composition:

G. Potassium ferricyanide 100 Potassium bromide 15 Borax 2O Magnesiumsulfate 50 Water to 1000 cm. (pH: 8.6).

Rinsing is continued for another 10 minutes at 18 to 20 C. and then thematerial is fixed again for 5 minutes at 20 C. in a bath of thefollowing composition:

G. Sodium thiosulfate Borax 20 Magnesium sulfate 50 Water to 1000 cm.(pH: 8.9)..

Finally, rinsing is-continued for 10 minutes at 18 to 20 C. and thematerial is dried. The strip of finished light-sensitive color materialshows in addition to a cyan wedge 21 redmasking wedge of oppositegradation, by whichthe side-absorptions of the cyan image arecompensated.

EXAMPLE 2 To /2 kg. of a green-sensitive silver'bromo-iodide (2% iodide)emulsion containing mol ofsilverhalide is added an alcoholic solution of6 g. of 1-(4-sulfophenyl)- 3-pentadecyl-pyrazolone-(5), preparedanalogously to the method of Example 2 of British specification 502,665,and 2 g. of N ,N -cyclodiethylene oxide-N -hexadecyb sulfonylbenzamidrazone prepared according to Preparation 4. After-adding theusual additives the emulsion is coated, exposed, developed and furthertreated as indicated in Example 1. The finished strip shows in additionto a magenta wedge a yellow masking wedge of opposite gradation reducingthe disturbing influence of the side adsorption in the formed magentaimage.

EXAMPLE 3 To /2 kg. of a red-sensitive bromo-iodide emulsion (3% iodide)containing /6 mol of silver halide are added: (1) 9 g. of N (6'-cetylsu1fonyplheny) l hydroxy 2- naphthoic acid amide-3'-sodiumsulfonate dissolved in a mixture of 193 cm. of water and 7 cm. ofaqueous 2 N sodium hydroxide, and (2) 6 g. of the mask compound preparedaccording to Preparation 11, dissolved in a mixture of 6 cm. of 2 Nsodium hydroxide,.6 cm. of ethanol and 18 cm. of distilled water. Afteracidification to pH 6, the usual additives such as hardeners, wettingagents and stabilizers and the necessary quantity of distilled water areaddedto the emulsion in order to obtain 1 kg. of flowable emulsion. Theemulsion is coated on a suit- 21 ablesupport and-dried. After exposurethrough a greywedge with a constant 0.15, the photographic materialcomposed in this way is developed and further treated as in Example 1.In the exposed and processed strip, in addition to a cyan image also anorange to yellow mask image is formed, with a gradation opposed to thatof the cyan image, and which compensates the side-absorptions of thecyan image in the blue as well as in the green region of the spectrum.

EXAMPLE 4.

To /2 kg. of .a red-sensitive bromo-iodide emulsion (3% iodide)containing mol of silver halide are added: (1) 9 g. ofN-(6-n-hexadecylsulfonylphenyl)-1-hydroxy- Z-naphthoic acidamide-3-sodium sulfonate dissolved in a mixture of 193 cm. of water and7 cm. of aqueous 2 N sodium hydroxide, and (2) 6. g. of the maskcompound prepared according to Preparation 4, dissolved in a mixture of12 cm. of 2 N sodium hydroxide and 18 cm. of ethanol. Afteracidification to pH 6, the usual additives such as hardeners, wettingagents and stabilizers, and the necessary quantity of distilled waterare added to the emulsion in order to obtain 1 kg. of flowable emulsion.The emulsion is coated on a suitable support and dried. After exposurethrough a grey-wedge with a constant 0.15, the photographic materialcomposed in this way is developed and further treated as in Example 1.In the exposed .and processed strip, in addition to a cyan image also anorange to yellow mask image is formed, with a gradation opposed to thatof the cyan image, and which compensates the side-absorptions of thecyan image chiefly in the blue region of the spectrum.

EXAMPLE 5 To /2 kg. of a red-sensitive =bromo-iodide emulsion (3%iodide) containing mol of silver halide .are added: (1) 9 g. of N-(6f-nhexadecylsulfonyphenyl)-1-hydr.oxy- Z-naphthoic acid amide-3-sodiumsulfonate dissolved in a mixture of 193 cm. of water and 7 cm. ofaqueous 2 N sodium hydroxide, and (2) 6 g. of the mask compound preparedaccording to Preparation 9, dissolved in a mixture of 6 cm. of 2 -Nsodium hydroxide, 6 cm. of ethanol and 18 cm? of distilled water. Afteracidification to pH 6, the usual additives such as hardeners, wettingagents and stabilizers and the necessary quantity of distilled water areadded to the emulsion in order to obtain 1 kg. of flowable emulsion. Theemulsion is coated on a suitable support and dried. After exposurethrough a greywedge with a constant 0.15, the photographic materialcomposed in this way is developed and further treated as in Example 1.In the exposed and processed strip, in addition to a cyan image also anorange to yellow mask image is. formed, with a. gradation opposed tothat of the cyan image, and which compensates the side-absorption of thecyan image in the blue as well as in the green region of the. spectrum.

EXAMPLE 6 To /2 kg. of .a red-sensitive bromo-iodide emulsion (3%iodide) containing Amol of silver halide are added: (1) 9' g. ofN-(6-n-hexadecylsulfonylphenyl-1-hydroxy-2- naphthoic acidamide-3-sodium sulfonates dissolved in a mixture of 193 cm. of water and7 cm. of aqueous 2 N sodium hydroxide, and (2) 2 g. of the mask compoundprepared according -to Preparation 7, dissolved in a mixture of 17.5 cm.of diacetone alcohol and 2.5 cm. of alcoholic N/2 sodium hydroxide.After acidification to pH 6, the usual additives such as hardeners,wetting agents and stabilizers and the necessary quantity of distilledwater are added to the emulsion in order to obtain 1 kg. of flowableemulsion. The emulsion is coated on a suitable support and dried. Afterexposure through a grey-wedge With a constant 0.15, the photographicmaterial composed this way is developed. and further treated as inExample 1. Inthe exposed and processed strip, in addition to a cyanimage also an orange one is formed, with a gradation opposed to that ofthe cyan image, and which compensates the side-absorptions of the cyanimage in the blue as well as in the green region of the spectrum.

EXAMPLE 7 To /2 kg. of a red-sensitive bromo-iodide emulsion (3% iodide)containing /6 mol of silver halide are added: (1) 9 g. ofN-(6-n-hexadecylsulfonylphenyl)-1- hydroxy-2rnaphthoic acidamide-3'-sodium sulfonate dissolved in a mixture of 193 cm. of Water and7 cm. of aqueous 2 N sodium hydroxide, and (2) 6 g. of the mask compoundprepared according to Preparation 8, dissolved in a mixture of 6 cm. of2 N sodium hydroxide and 24 cm. of ethanol. After acidification to pH 6the usual additives such as hardeners, wetting agents and stabilizersand the necessary quantity of distilled water are added to the emulsionin order to obtain 1 kg. of flowable emulsion. The emulsion is coated ona suitable support and dried. After exposure through a greyawedge with aconstant 0.15, the photographic material composed in this way isdeveloped and further treated as in Example 1. In the exposed andprocessed strip, in addition to a cyan image also an orange to magentamask image is formed, with a gradation opposed to that of the cyanimage, and which compensates the side-absorptions of the cyan image inthe blue and the green region of the spectrum.

EXAMPLE 8 To /2 kg. of a red-sensitive bromo-iodide emulsion (3% iodide)containing /6 mol of silver halide are added: (1) 9 g. ofN-(6'-n-hexadecylsulfonylphenyl)-1-hydroxy- 2-naphthoic acidamide-3'-sodium sulfonate dissolved in a mixture of 193 cm. of Water and7 cm. of aqueous 2 N sodium hydroxide, and (2) 3 g. of the mask compoundprepared according to Preparation 6, dissolved in a mixture of 3 cm. of2 N sodium hydroxide, 3 cm. of ethanol, and 9 cm? of distilled water.After acidification to pH 6, the usual additives such as hardeners,wetting agents and stabilizers, and the necessary quantity of distilledwater are added to the emulsion in order to obtain 1 kg. of flowableemulsion. The emulsion is coated on a suitable support and dried. Afterexposure through a grey-wedge With a constant 0.15, the photographicmaterial composed in this way is developed and further treated as inExample 1. In the exposed and processed strip, in addition to a cyanimage also an orange to magenta mask image is formed, with a gradationopposed to that of the cyan image, and which compensates theside-absorptions of the cyan image in the blue and the green regions ofthe spectrum.

EXAMPLE 9 To a /2 kg. of red-sensitive silver bromo-iodide emulsion (2%iodide) containing /6 mol of silver halide are added: (1) 10 g. ofN-(6-n-hexadecylsulfonylphenyl)-lhydroxy-Z-naphthoic acid amide-3-sodiumsulfonate dissolved in a mixture of 193 cm. of Water and 7 cm. ofaqueous 2 N sodium hydroxide, and (2) 6 g. of the mask compound preparedaccording to Preparation 11, dissolved in a mixture of 6 cm. of 2 N.sodium hydroxide, 6 cm. of ethanol and 18 cm. of distilled Water. Afteracidification to pH 6, the usual additives such as hardeners, wettingagents and stabilizers, and the necessary quantity of distilled waterare added to the emulsion in order to obtain 1 kg. of flowable emulsion.After coating this emulsion forms part of a multilayer photographicmaterial consisting of the following superposed layers in the indicatedsequence: a support, an anti-halation layer, a gelatin insulating layer,the above-mentioned red-sensitive emulsion.

layer containing a color coupler for cyan, a gelatin. interlayer, agreen sensitive emulsion layer containing a color coupler for magenta, ayellow filter layer, a blue-sensitive emulsion layer containing a colorcoupler for yellow and at last a gelatin overcoat as antistres layer.After exposure through a grey-Wedge the photographic material isdeveloped and further treated as in Eaxmple 1. A

23 mainly cyan-colored image is obtained together with an orange toyellow dye image in the red-sensitive layer, said orange to yellow dyeimage being of opposite gradation in respect of the cyan dye image andcompensating the side-absorption of the cyan image in the blue as wellas in the green region of the spectrum.

EXAMPLE A photographic multilayer material consisting of the followingsuperposed layers in the indicated sequence: a support, an anti-halationlayer, a gelatin insulating layer, a red-sensitive emulsion layercontaining a color coupler for cyan, a gelatin interlayer, agreen-sensitive emulsion layer containing a color coupler for magenta, ayellow filter layer, a blue-sensitive emulsion layer containing a colorcoupler for yellow and at last a gelatin overcoat as antistress layer.The red-sensitive emulsion layer is coated starting from ared-sensitized gelatino silver bromo-iodide emulsion. This emulsion isprepared as follows: to /2 kg. of a gelatino silver bromo-iodideemulsion (2% iodide) containing mol of silver halide are added: (1) 9 g.of N-(6-n-hexadecylsulfonylphenyl)-lhydroxy-Z-naphthoic acidamide-3'-sodium sulfonate dissolved in a mixture of 175 cm. of water and6.3 cm. of aqueous 2 N sodium hydroxide, and (2) 6 g. of the maskcompound prepared according to Preparation 11, dissolved in a mixture of6 cm. of 2 N sodium hydroxide, 6 cm. of ethanol and 18 cm. of distilledwater. Next, this emulsion is acidified with acetic acid to pH 6, andafter adding the usual additives such as hardeners, wetting agents,stabilizers and the necessary quantity of distilled water, 1 kg. offiowable emulsion is obtained. The greensensitive emulsion layer iscoated starting from a greensensitized gelatino silver bromo-iodideemulsion. This emulsion is prepared by adding to /2 kg. of gelatinosilver bromo-iodide emulsion (2% iodide) containing /6 mol of silverhalide, 9 g. of a slightly alkaline alcoholic solution of2-(l-phenyl-5-oxo-3-pyrazolinylimino)-3-carbethoxyr4-p-(1-nhexadecyloxy)-phenyl-thiazoline, 6- g. of the mask compound3-ethyl-2-benzothiazolone-B-n-hexadecylsulfonyl hydrazone preparedaccording to our British patent specification No. 975,932 and having thefollowing formula:

and dissolved by heating in a mixture of alcohol and water (1:3) with alittle sodium hydroxide, acidifying with acetic acid to pH 6, and addingthe usual additives such as hardeners, wetting agents, stabilizers andthe necessary quantity of distilled water to obtain 1 kg. of flowableemulsion. The light sensitive multilayer photographic material isexposed through a grey-wedge, de-v veloped and further treated asdescribed in Example 1.

In the red-sensitive emulsion layer in addition to a cyan To /2 kg. of ared-sensitive broino-iodide emulsion (3% of iodide) containing /6 mol ofsilver halide are added: (1) 10 g. of N-(6'-n-hexadecylsulfonyl-phenyl)-1-hydroxy-2-naphthoic acid amide-3-sodium sultonate dissolved in amixture of 193 cm. of water and 7 cm.

of aqueous 2 N sodium hydroxide, and. (2) '5 g. of the mask compoundprepared according to Preparation 12, dissolved in a mixture of 37.5 cm.of water and 12.5 cm. N sodium hydroxide. After acidification withacetic acid to pH 6, the usual additives such as hardeners, wettingagents and stabilizers and the necessary quantity of distilled water areadded to the emulsion in order to obtain 1 kg. of fiowable emulsion. Theemulsion is coated on a suitable support and dried. After exposurethrough-a grey-wedge with a constant. 0.15, the photographic materialcomposed in this way is developed and further treated as in Example 1.In the exposedand processed strip, in addition toa cyan image .also anorange mask image is formed, with a gradation opposed to that of thecyan image, and which compensates the side-absorptions of the cyan imagein the blue as well as in the green region of the spectrum.

We claim:

1. In a method of forming a color corrected image in a photographicelement having at least one silver halide emulsion layer containing acolor coupler for magenta which is reactive with the oxidation product.of an aromatic amino developing agent-to form by color development amagenta primary dye image which absorbs a major proportion of light inone region of the visible spectrum, and undesirably absorbs a minorproportion of light in at least one other region of the visiblespectrum, in which method said element is exposed to said image to bephotographed, developed with'said developing agent and thereaftertreated with an oxidizing solution, the improvement wherein said elementhas present therein a mask-forming compound having the formula:

wherein R is a member of the group consisting of a hydrogen atom and anacyl radical,

R is a member of the group consistingof a hydrogen atom, an'aminoradical, an alkyl radical, an alkylene radical, an aryl radical, and aheterocyclic radical,

Y represents the non-metallic atoms necessary to complete anitrogen-containing heterocyclic nucleus, and

X is a member of the group consisting of an hydroxyl radical, an aminoradica1,=an aliphatic hydrocarbon radical, an aryl radical, and aheterocyclic radical; whereby the residual color coupler oxidativelycouples with said mask-forming compound to form a secondary dye imagehaving a gradation opposite to that of said magenta primary dye image,said secondary .image absorbing regions but transmitting substantiallyall the light in said-major absorption region.

2. The method of claim 1 wherein said color coupler for magenta is amember of the group consisting of the indazolone and pyrazolone colorcouplers.

3. The method of claim 1 wherein said oxidizing solution is aphotographic bleaching bath.

4. The method of claim 1 wherein said mask-forming compound ispresent inat least said one emulsion layer.

5. The method of claim 2 wherein said mask-forming compound forms ayellow secondary dye image.

6. A color photographic element useful in the method of claim 1, saidelement having superposed silver halide emulsion layers sensitive todiiferent regions of the visible spectrum, at least one of said layerscontaining a color coupler for magenta which is reactive with theoxidation product of an aromatic amino developing agent to form by colordevelopment a magenta primary dye image which absorbs a major proportionof light in' one region of the spectrum, and undmirably absorbs a minorpro portion of light in at least one other region of the 25' visiblespectrum, such layer also containing a mask-forming compound-of theformula:

I" Il a I'M t t t sozx wherein R is a member of the group consisting ofa hydrogen atom and an acyl radical,

Y represents the non-metallic atoms necessary to complete anitrogen-containing heterocyclic nucleus,

R is a member of the group consisting of a hydrogen atom; an aminoradical, an alkyl radical, an alkylene radical, an aryl radical, and aheterocyclic radical, and

X is a member of the group consisting of an hydroxyl radical, an aminoradical, an aliphatic hydrocarbon radical, an aryl radical, and aheterocyclic radical;

said color coupler for magenta also being reactive with the oxidationproduct of said mask-forming compound to form a secondary dye imagehaving a gradation opposite to that of said magenta primary dye image,and absorbing light in at least one of said unwanted minor absorptionregions but transmitting substantially all the light in said majorabsorption region.

7. The element of claim 6 wherein said color coupler for magenta is amember of the group consisting of the indazolone and pyrazolone colorcouplers.

8. In a method of forming a color corrected image in a photographicelement having at least one silver halide emulsion layer containing acolor coupler for cyan which is reactive with the oxidation product ofan aromatic amino developing agent to form by color development a cyanprimary dye image which absorbs a major proportion of light in oneregion of the visible spectrum, and undesirably absorbs a minorproportion of light in at least one other region of the visiblespectrum, in which method said element is exposed to said image to bephotographed, developed with said developing agent and thereaftertreated with an oxidizing solution, the improvement wherein said elementhas present therein a masktorming compound having a formula selectedfrom the group consisting of:

R is a member of the group consisting of a hydrogen atom and an acylradical,

R is a member of the group consisting of a hydrogen atom, an aminoradical, an alkyl radical, an alkylene radical, an aryl radical, and aheterocyclic radical,

R and R are each a member of the group consisting of a hydrogen atom, analkyl radical, and an aryl radical,

Y represents the non-metallic atoms necessary to complete anitrogen-containing heterocyclic nucleus, and

X is a member of the group consisting of an hydroxyl radical, an aminoradical, an aliphatic hydrogen radical, an aryl radical, and ahetercyclic radical;

whereby the residual color coupler oxidatively couples with saidmask-forming compound to form a secondary dye image having a gradationopposite to that of said cyan primary dye image, said secondary imageabsorbing light in at least one of said undesirable minor absorptionregions but transmitting substantially all the light in said majorabsorption region.

9. The method of claim 8 wherein said color coupler 26 for cyan is amember of the group consisting o-tthe phenol and naphthol colorcouplers.

19. The method of claim 9' wherein said, color coupler has the formula:

({)II IIQD wherein:

X is a radical of the group consisting of O', -S-,

and SO Z is a member of the group consisting of a hydrogen atom and ahalogen atom,

D is an aliphatic radical comprising a linear chain-of 5-20 carbonatoms, and

M is a member of the group consisting of a hydrogen atom, an alkaliatom, and an ammonium group.

1 1. The method of claim 8 wherein said oxidizing bath is a photographicbleaching bath.

12. The method of claim 8 wherein said mask-forming compound is presentin the same emulsion layer containing said colo-r coupler.

13. The method of claim 9 wherein said mask-forming compound forms .ayellow-to-magenta secondary dye image.

'14. A color photographic element useful in the method of claim 8, saidelement having superposed silver halide emulsion layers sensitive todiiferent regions of the visible spectrum, at least one of said layerscontaining a color coupler for cyan which is reactive with the oxidationproduct of an aromatic amino developing agent to form by colordevelopment a cyan primary dye image which absorbs a major proportion oflight in one region of the spectrum, and undesirably absorbs a minorproportion of light in at least one other region of the visiblespectrum, such layer also containing a mask-forming compound of aformula selected from the group consisting of:

wherein:

R is a member of the group consisting of a hydrogen atom and an acylradical,

Y represents the non-metallic atoms necessary to complete anitrogen-containing hetero-cyclic nucleus,

R is a member of the group consisting of a hydrogenation, an aminoradical, an alkyl radical, an alkylene radical, an aryl radical, and aheterocyclic radical,

R and R are each selected :from the group consisting of a hydrogen atom,an alkyl radical, and an aryl radical, and

X is a member of the group consisting of an hydroxyl radical, an aminoradical, an aliphatic hydrogen radical, an aryl radical, and aheterocyclic radical;

said color coupler for magenta also being reactive with the oxidationproduct of said mask-forming compound to form a secondary dye imagehaving a gradation opposite to that of said cyan primary dye image, andabsorbing light in at least one of said unwanted minor absorptionwherein:

X is a radical of the group consisting of O,

Z is a member of the group consisting of a hydrogen atom and a halogenatom,

D is an aliphatic radical comprising a linear chain of 520 carbon atoms,and

M is a member of the group consisting of a hydrogen atom, an alkaliatom, and an ammonium group.

References Cited by the Examiner UNITED STATES PATENTS 2/1950 Hanford 9655 8/1950 Young 96-55 2/ 1958 Jennen 96-10() 8/1961 Lofiler etal. 96912/1-961 De 'Ramaix et al. 96-9 12/1961 De Ramaix 9655 X 7/ 1962 DeRa'rnaix et a1. 969

FOREIGN PATENTS 12/1-952 Great Britain. 2/1958 Great Britain.

NORMAN G. TORCHIN, Primary Examiner.

20 HAROLD N. BU'RSTEI-N, Examiner.

R. A. BURROUGHS, J. T. BROWN,

Assistant Examiners.

1. IN A METHOD OF FORMING A COLOR CORRECTED IMAGE IN A PHOTOGRAPHICELEMENT HAVING AT LEAST ONE SILVER HALIDE EMULSION LAYER CONTAINING ACOLOR COUPLER FOR MAGENTA WHICH IS REACTIVE WITH THE OXIDATION PRODUCTOF AN AROMATIC AMINO DEVELOPING AGENT TO FORM BY COLOR DEVEOP MENT AMAGENTA PRIMARY DYE IMAGE WHICH ABSORBS A MAJOR PROPORTION OF LIGHT INONE REGION OF THE VISIBLE SPECTRUM, AND UNDESIRABLY ABSORBS A MINORPROPORTION OF LIGHT IN AT LEAST ONE OTHER REGION OF THE VISIBLESPECTRUM, IN WHICH METHOD SAID ELEMENT IS EXPOSED TO SAID IMAGE TO BEPHOTOGRAPHED, DEVELOPED WITH SAID DEVELOPING AGENT AND THEREAFTERTREATED WITH AN OXIDIZING SOLUTION, THE IMPROVEMENT WHEREIN SAID ELEMENTHAS PRESENT THEREIN A MASK-FORMING COMPOUND HAVING THE FORMULA: